CN108732151A - There is the preparation of luminous gold nanoparticle and its rapid analysis and test method of highly sensitive optic response for volatile amine - Google Patents
There is the preparation of luminous gold nanoparticle and its rapid analysis and test method of highly sensitive optic response for volatile amine Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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Abstract
The invention discloses there is the luminous gold nanoparticle of highly sensitive optic response to prepare for volatile amine and its rapid analysis and test method, it is related to a kind of double emission ratios optical analysis techniques.Preparation method includes the following steps：Compound containing sulfydryl is mixed in a solvent with gold chloride, reducing agent, alkali, 25-95 DEG C of stirring 1-24 h, then ultrafiltration is centrifuged off solution small molecular impurity, then freeze-dried concentration, obtains the luminous gold nanoparticle.Luminous gold nanoparticle is also applied to the highly sensitive optical detection of volatility amine compound by the present invention, and detection limits low, fast and stable, and can be generated double-colored transmitting and be carried out ratio optical analysis, and stability high interference is small.Preparation method of the present invention is simple, at low cost, is easy to industrialized production.The luminous gold nanoparticle that the present invention synthesizes in the solution, through absorbing the amine substance of dissolving various concentration, can obviously observe that nanogold gradually generates dual color light emitting by single shine, generate the gold nanoparticle of dual wavelength transmitting.
Description
Technical field
The invention belongs to function optical nano Material Fields, and in particular to have highly sensitive optic response for volatile amine
Luminous gold nanoparticle prepare and its rapid analysis and test method.
Background technology
Fluorescence analysis method and with its imaging technique with its high sensitivity, it is reproducible and easy to operate the features such as,
As a kind of important tool (Mater.Today in the area researches such as bio-sensing, medical diagnosis and food product environment safety
2013,16, 477；J.Am.Chem.Soc., 2016,138,6380), therefore fluorescence of the synthesis with highly sensitive optic response is visited
Needle has great importance and practical value.In recent years, luminescent metal nano-particle is because it is with extra small size and unique
Optical property shows great application prospect in fields such as biological detection, medicine, industry manufactures.The table of luminous gold nanoparticle
Face chemistry and optics regulation and control method by further expand its in optical sensing field application range (J.Am.Chem.Soc.,
2013,135, 4978；Angew.Chem.Int.Ed.,2013,52,12572；Nat.Nanotechnol.,2017,12,
1096).For example, the Murray seminar in North Carolina, USA university church mountain branch school utilizes different surfaces reagent such as benzene second sulphur
Alcohol, triphenylphosphine and Tiopronin etc. synthesize a series of grain sizes<The luminous Jenner of (800nm -1.3 μm) of near-infrared wavelength of 2nm
Rice corpuscles (AuNPs) (J.Am.Chem.Soc., 2005,127,812), they point out that this is a kind of and nano-particles size energy
The unrelated metal local electronic surface state of grade shines；Nienhaus seminar of the Karlsruhe, Germany Institute of Technology utilizes lipoic acid
It prepares the AuNPs of near-infrared luminous (710nm) of responsive to temperature type and is applied to intracellular temperature detection
(Angew.Chem.Int.Ed., 2013,52,11154).Currently, based on single wavelength transmitting AuNPs design and develop and
Application progress well is achieved in terms of its analyzing detecting method.
Fluorescent nano probe to be made is realized in analyzing detection field and is more widely applied, and is studied to utilize with design and be visited
Double fluorescence emission wavelengths that needle is generated with analyte interaction seem particularly to carry out the ratio fluorescent probe of self-correction
It is important.At this stage, a variety of methods have been developed to regulate and control to the emission wavelength of gold nanoparticle.Such as regulate and control gold nanoparticle
The ligand density of surface modification changes the content of nanoparticle surface Au (I), to change the emission wavelength of nanogold
(Angew. Chem.Int.Ed.,2016,55,8894)；In addition, introducing other metal ions in the table of gold nanoparticle that shines
Face nanometer generates new launching centre, such as by Ag+It is introduced into the nanogold of the 810nm transmittings of glutathione modification and generates newly
705nm launching centres (J.Phys.Chem.Lett., 2018,9,557)；In addition, the mixed electronic states of S-Au-S-Au-S semi-rings
Regulation and control near infrared region transmitting can be also participated in including metal reagent electric charge transfer, charge and surface reagent are near infrared emission wavelength
There is important influence (J.Phys.Chem.C, 2010,114,19935) with the photoluminescence quantum yield of gold nanoparticle.
Most of volatility amine compound has strong corrosive and putrefactive odor, such as methylamine, ethamine and ethylenediamine.Air
The amine steam of middle high-content generates stimulation to human body eye mask and nose larynx, influences health.Therefore, the volatility in environment is monitored
Aminated compounds is of great significance in Chemical Manufacture and environmental protection etc..The utilization chemical emissions fluoroscopic examination reported
Volatile amine method have it is more a variety of, such as using nitrogen-containing group promote hydroxyphenyl quinazoline generate aggtegation induced fluorescence generate
(AIE) detection volatile amine substance (Acs Sensors, 2016,1,179)；Or it is a kind of with multi-layer structure by synthesizing
SnS2Small-molecule probe captures the ammonia molecule (Sens.Actuator B-Chem.2018,262,771) in air；Also it grinds
36 hole fluorescence sequence plate methods of designing are studied carefully by differentiating tested substance electron density energy 30 kinds of organic amine compounds of Accurate classification
(Anal.Chem.,2018,90,4815).However, these detection methods are only applicable to the single wave of unstressed configuration background interference at present
Long chemical detection, and fluorescence probe fluorescence intensity, stability, concentration and excitation light source are suffered from analyte detection process
The interference that many factors such as stability influence.Therefore, using the gold nanoparticle that shines as probe, pair of design and development volatile amine
Wavelength ratio detection method can further increase sensitivity and the stability of volatile amine detection, with more actually detected
Application value.
Invention content
In order to overcome the disadvantages and deficiencies of the prior art, the object of the present invention is to provide have height for volatile amine
The luminous gold nanoparticle of sensitive optical response prepares and its rapid analysis method.Quick analytical technology provided by the invention, can
By a variety of analysis means Simultaneous Monitorings, including uses Fluorescence Spectrometer detection nanoparticle fluorescence Strength Changes, uses optics
Imaging system detects nanoparticle fluorescence intensity and its imaging of dual wavelength ratio, while can also pass through human eye observation's red light intensity
Variation carries out Visual retrieval.
The purpose of the present invention is realized by following technical solution.
For volatile amine there is the luminous gold nanoparticle preparation of highly sensitive optic response and its volatile amine quickly to divide
Analysis method, preparation method and analyte detection process are as follows：
There is the preparation method of the luminous gold nanoparticle of highly sensitive optic response, including following mistake for volatile amine
Journey：
Mercaptan micromolecular compound, gold chloride, reducing agent, alkali and solvent are mixed, stirring, then is centrifuged off with ultrafiltration residual
Remaining small molecule or ionic compound, then freeze-dried to be concentrated into brown yellow solution, room temperature preservation obtains luminescent gold nanoparticle
Son.
Further：The whipping temp is 25-95 DEG C, mixing time 1-24h；The luminous gold nanometer particle grain size
For 1-3nm.
Further, the mercaptan micromolecular compound is thioacetic acid, mercapto succinic acid, thiohydracrylic acid, half Guang ammonia
Acid, or be the compound with following chemical structural formula：
R-SH
In formula, R is containing amino, carboxyl or sulfonic alkyl chain or heterocycle compound.
Further, the mixing that the mercaptan micromolecular compound, gold chloride, reducing agent, alkali and solvent are mixed to get is molten
In liquid, the concentration ratio of gold chloride and mercaptan micromolecular compound is 1:0.3 to 1:3；Reducing agent and mercaptan micromolecular compound
Concentration ratio is less than 1.
Further, the reducing agent is in sodium borohydride, sodium citrate, ascorbic acid, dimethylamine borane or hydrogen
More than one, wherein the pressure of hydrogen is 1-50 atmospheric pressure.
Further, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, alkali soluble
Liquid pH value is 7-14；The solvent is one or more of ethyl alcohol, methanol, acetone, glycerine, toluene or water.
Further, the ultrafiltration centrifugation is at 10-37 DEG C, is washing lotion, ultrafiltration fenestra with the distilled water of pH=7-14
Diameter is 3-50kDa, centrifugal force 10000-20000g.
The present invention also provides the sides that the gold nanoparticle obtained by above-mentioned preparation method quickly analyzes detection volatile amine
Method includes the following steps：Luminous gold nanoparticle is diluted in water and forms the solution of gold nanoparticles that shines, adds volatility
Amine gas aqueous solution, or luminous solution of gold nanoparticles is exposed in volatile amine gas, observe by the naked eye luminous change
Change, Fluorescence Spectrometer detection solution fluorescence changes and is changed using imaging system observation solution fluorescence.
Further, the volatile amine gas includes ammonia, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, three second
One or more of amine, propylamine or ethylenediamine.
Further, the pH value of the luminous solution of gold nanoparticles is 7-12.
Further, the gold nanoparticle, which quickly analyzes detection volatile amine, is carried out at a temperature of 25-37 DEG C.
After the near-infrared luminous gold nanoparticle dissolving in a solvent that the present invention synthesizes, pH value is adjusted, and molten in the solution
The aminated compounds for solving various concentration reuses Fluorescence Spectrometer and fluoroscopic imaging systems detection, and can obviously observe can
See that area's feux rouges generates and increases with the amine substance concentration of dissolving and enhance, and observes that near infrared luminous intensity weakens simultaneously.
Using detection optics dynamic range and fluorescence intensity ratio of the feux rouges near infrared light is calculated, is realized a kind of simple, efficient, steady
Fixed ratio imaging detection method, reduces the interference of other optical signallings, is answered as environment probe to further realize nanogold
With theoretical and experiment basis has been established, have emphatically in fields such as environmental analysis detection, optical sensing and Development of Novel photoelectric materials
The application wanted.
Compared with prior art, the invention has the advantages that and technique effect：
(1) the gold nanoparticle fluorescence probe that the present invention synthesizes, synthesis technology is simple, and energy consumption is low, of low cost, is easy to big
Technical scale metaplasia is produced.
(2) detection method that the present invention uses is simple, quick, stable, detection limit is low, probe and analyte interaction
After realize double-colored light emitting obtain ratio imaging eliminate other optical signallings interference, be readily applied to actual sample detection.
(3) detection means that the present invention uses can be realized through a variety of ways, including visually observe, Fluorescence Spectrometer detection
It is observed with imaging system.
Description of the drawings
Fig. 1 is excitation, transmitting and the abosrption spectrogram for the gold nanoparticle that embodiment 1 synthesizes.
Fig. 2 is the x-ray photoelectron spectroscopy figure for the gold nanoparticle that embodiment 1 synthesizes.
Fig. 3 is the gold nanoparticle infrared spectrogram that embodiment 1 synthesizes.
Fig. 4 is fluorescent stability result of study figure of the luminous gold nanoparticle of the synthesis of embodiment 1 under condition of different pH.
Fig. 5 is the transmission electron microscopy that the luminous gold nanoparticle that embodiment 1 synthesizes is in deionized water dispersity
Mirror figure.
Fig. 6 a are the fluorescence that the luminous gold nanoparticle that embodiment 1 synthesizes is used to detect various concentration volatile amine substance
Change spectrogram.
Fig. 6 b are the change in fluorescence that the luminous gold nanoparticle that embodiment 1 synthesizes detects various concentration volatile amine substance
Ratio image.
Fig. 7 is excitation, transmitting and the abosrption spectrogram of product in 2 building-up process of embodiment.
Fig. 8 is fluorescent stability result of study figure of the luminous gold nanoparticle of the synthesis of embodiment 2 under condition of different pH.
Fig. 9 is the fluorescence that the luminous gold nanoparticle that embodiment 2 synthesizes is used to detect various concentration volatile amine substance
Change spectrogram.
Figure 10 is excitation, transmitting and the abosrption spectrogram of product in 3 building-up process of embodiment.
Figure 11 is the transmission electron microscopy that the luminous gold nanoparticle that embodiment 3 synthesizes is in deionized water dispersity
Mirror figure.
Figure 12 a are that the luminous gold nanoparticle that embodiment 3 synthesizes is used to detect same concentration variety classes volatility amine
The change in fluorescence spectrogram of substance.
Figure 12 b are that the luminous gold nanoparticle that embodiment 3 synthesizes detects same concentration variety classes volatile amine substance
Change in fluorescence ratio chart.
Figure 13 is excitation, transmitting and the abosrption spectrogram of product in 4 building-up process of embodiment.
Figure 14 is the change in fluorescence comparison diagram for the volatile amine substance that various concentration is added in 4 detection process of embodiment.
Figure 15 is the change in fluorescence comparison diagram for the volatile amine substance that various concentration is added in 5 detection process of embodiment.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.It is noted that if the following process for having not special detailed description, is that those skilled in the art can refer to the prior art
Realize or understand.
In specific embodiment, observation gold nanoparticle detects the instrument that the change in fluorescence that volatility amine compound generates uses
Device includes U.S. PerkinElmer fluorescent/phosphorescents/luminometer (LS-55) and U.S.'s Analytikjena imaging systems
(UVP ChemStudio PLUS 815) etc..
Embodiment 1
Under the conditions of room temperature (25 DEG C), 43mL deionized waters, 150 μ L aqueous solution of chloraurate are added into three-necked flask
(1M), 2.1mL thiohydracrylic acids aqueous solution (0.1M), 5mL sodium hydrate aqueous solutions (1M), are vigorously stirred, are then slowly added dropwise
Sodium borohydride aqueous solution (1 μM) becomes brown color to solution, continues to stop after being stirred to react 1h, the use of molecular cut off is 3k's
Ultra-filtration centrifuge tube ultrafiltration centrifuges, and is cleaning solution with deionized water, and cleaning 3 times or more removes small molecule and ion, then passes through freezing
Dry concentration, obtains target product.Products therefrom is diluted again in aqueous solution, various concentration volatile amine is dissolved in this
Gold nanoparticle aqueous solution detects change in fluorescence using fluophotometer and imaging system.
The product maximum emission peak of synthesis is in 800nm or more, such as Fig. 1.
The x-ray photoelectron spectroscopy figure of the luminous gold nanoparticle of synthesis, such as Fig. 2, in the luminous gold nanoparticle of synthesis
Valence state containing higher proportion is monovalence gold element, can be higher than 35%.
The ligand modified of luminous gold nanoparticle of synthesis is applied to gold nanoparticle surface, such as Fig. 3, sulphur by-SH keys
After the modification to gold nano surface of alcohols micromolecular compound, sulfydryl vibration peak disappears.
The luminous gold nanoparticle of synthesis equal energy stabilized illumination, such as Fig. 4 under condition of different pH.
The grain size of the luminous gold nanoparticle of synthesis is 1-3nm, such as Fig. 5.
Volatility amine is dissolved in gold nano aqueous solution, and launching light spectrogram display generates new emission peak, such as Fig. 6 a.
Volatility amine is dissolved in gold nano aqueous solution, has the generation of visual field feux rouges, and near infrared luminous intensity subtracts
It is weak, such as Fig. 6 b, ethylenediamine concentration in figure：0→100mM.
Embodiment 2
Under the conditions of oil bath (95 DEG C), 43mL deionized waters, 150 μ L aqueous solution of chloraurate (1 are added into three-necked flask
M), 3mL thioacetic acid aqueous solution (0.1M), 5mL sodium hydrate aqueous solutions (1M), are vigorously stirred, citric acid are then slowly added dropwise
Sodium water solution (1 μM) becomes glassy yellow to solution, continues to be stirred to react, and stops being stirred to react for 24 hours afterwards, is using molecular cut off
The ultra-filtration centrifuge tube ultrafiltration of 3k centrifuges, and is cleaning solution with deionized water, and cleaning 3 times or more removes small molecule and ion, then passes through
Freeze-drying concentration, obtains target product.Products therefrom is diluted again in aqueous solution, various concentration volatile amine is dissolved
In the gold nanoparticle aqueous solution, change in fluorescence is detected using fluophotometer and imaging system.
The luminous gold nanoparticle of synthesis has maximum emission peak, such as Fig. 7 at 600nm.
The luminous gold nanoparticle of synthesis can be stabilized under condition of different pH, such as Fig. 8.
The luminous gold nanoparticle of synthesis is for detecting volatile amine substance, and fluorescence intensity significantly increases at 600nm,
Such as Fig. 9.
Embodiment 3
Under the conditions of oil bath (95 DEG C), 43mL deionized waters, 150 μ L aqueous solution of chloraurate are added into three-necked flask
(1M), 1mL aqueous cystein solutions (0.1M), 5mL sodium hydrate aqueous solutions (1M), are vigorously stirred, boron hydrogen are then slowly added dropwise
Change sodium water solution (1 μM) becomes glassy yellow to solution, continues to stop after being stirred to react 3h, uses the ultrafiltration that molecular cut off is 3k
Centrifuge tube ultrafiltration centrifuges, and is cleaning solution with deionized water, and cleaning 3 times or more removes small molecule and ion, then passes through freeze-drying
Concentration, obtains target product.Products therefrom is diluted again in aqueous solution, by the variety classes volatile amine of same concentrations
(including ammonium hydroxide, dimethylamine, diethylamine, triethylamine, ethylenediamine and butanediamine etc.) is dissolved in the gold nanoparticle aqueous solution, uses
Fluophotometer and imaging system detect change in fluorescence.
The product maximum emission peak of synthesis is in 800nm or more, such as Figure 10.
The grain size of the luminous gold nanoparticle of synthesis is 1-3nm, such as Figure 11.
Different types of volatility amine is dissolved in gold nano aqueous solution, the new transmitting that launching light spectrogram display generates
Peak intensity is different, and the ratio of visible/near infrared luminous intensity also differs, such as Figure 12 a；Different types of volatility amine is molten
Solution has the visual field feux rouges of varying strength to generate, and near infrared luminous intensity weakens in gold nano aqueous solution, it can be seen that/
Near infrared luminous intensity ratio also differs, such as Figure 12 b.
Embodiment 4
Under the conditions of oil bath (95 DEG C), 43mL deionized waters, 150 μ L aqueous solution of chloraurate (1 are added into three-necked flask
M), 4.5mL mercaptosuccinics aqueous acid (0.1M), 5mL sodium hydrate aqueous solutions (1M), are vigorously stirred, boron are then slowly added dropwise
Sodium hydride aqueous solution (1 μM) becomes glassy yellow to solution, continues to stop after being stirred to react 6h, the use of molecular cut off is the super of 3k
Centrifuge tube ultrafiltration centrifugation is filtered, is cleaning solution with deionized water, cleaning 3 times or more removes small molecule and ion, then dry by freezing
Dry concentration, obtains target product.Products therefrom is diluted again in aqueous solution, various concentration volatile amine is dissolved in the gold
Nano-particle aqueous solution detects change in fluorescence using fluophotometer and imaging system.
The product maximum emission peak of synthesis is in 800nm or more, such as Figure 13.
Volatility amine is dissolved in gold nano aqueous solution, and launching light spectrogram display generates new emission peak, there is visual field
Feux rouges generates, and near infrared luminous intensity weakens such as Figure 14.
Embodiment 5
Under the conditions of 37 DEG C, 43mL deionized waters, 150 μ L aqueous solution of chloraurate (1M), 1.2 are added into three-necked flask
ML mercapto-polyglycols aqueous solution (0.1M, molecular weight 500-10000), is vigorously stirred, until solution becomes glassy yellow, continues to stir
Stop after mixing reaction 12h, is centrifuged using the ultra-filtration centrifuge tube ultrafiltration that molecular cut off is 3k, be cleaning solution with deionized water, clearly
It washes 3 times or more and removes small molecule and ion, then concentrated by being freeze-dried, obtain target product.Products therefrom is diluted again
In aqueous solution, various concentration volatile amine is dissolved in the gold nanoparticle aqueous solution, is using fluophotometer and imaging
System detection change in fluorescence.
Volatility amine is dissolved in gold nano aqueous solution, and launching light spectrogram display generates new emission peak, there is visual field
Feux rouges generates, and near infrared luminous intensity weakens such as Figure 15.
Examples detailed above is the preferable embodiment of the present invention, and wherein example 1 is optimal embodiment.But the reality of the present invention
The mode of applying is not restricted to the described embodiments, it is other it is any without departing from the spirit and principles of the present invention made by change
Become, modification, substitute, combination, simplify, should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. having the preparation method of the luminous gold nanoparticle of highly sensitive optic response for volatile amine, it is characterised in that：Packet
Include following procedure：
Mercaptan micromolecular compound, gold chloride, reducing agent, alkali and solvent are mixed, stirring, then is centrifuged off with ultrafiltration remaining small
Molecule or ionic compound, then freeze-dried to be concentrated into brown yellow solution, room temperature preservation obtains the gold nanoparticle that shines.
2. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：Mixeding liquid temperature is 25-95 DEG C when the stirring, mixing time 1-24h；The luminous gold nano
Particle diameter is 1-3nm.
3. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：The mercaptan micromolecular compound is thioacetic acid, mercapto succinic acid, thiohydracrylic acid, half Guang ammonia
Acid, or be the compound with following chemical structural formula：
R-SH
In formula, R is containing amino, carboxyl or sulfonic alkyl chain or heterocycle compound.
4. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：The mixed solution that the mercaptan micromolecular compound, gold chloride, reducing agent, alkali and solvent are mixed to get
In, the molar concentration rate of gold chloride and mercaptan micromolecular compound is 1:0.3 to 1：3；Reducing agent and mercaptan micromolecular compound
Molar concentration rate be less than 1.
5. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：The reducing agent is one in sodium borohydride, sodium citrate, ascorbic acid, dimethylamine borane or hydrogen
Kind or more, wherein the pressure of hydrogen is 1-50 atmospheric pressure.
6. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：The alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, aqueous slkali
PH value is 7-14；The solvent is one or more of ethyl alcohol, methanol, acetone, glycerine, toluene and water.
7. the preparation according to claim 1 for luminous gold nanoparticle of the volatile amine with highly sensitive optic response
Method, it is characterised in that：The ultrafiltration centrifugation is to use the distilled water of pH=7-14 for washing lotion at 10-37 DEG C, ultrafiltration fenestra
Diameter is 3-50kDa, centrifugal force 10000-20000g。
8. the gold nanoparticle obtained by any one of claim 1-7 preparation method quickly analyzes detection volatile amine
Method, it is characterised in that：Include the following steps：It is molten that luminous gold nanoparticle is diluted in the luminous gold nanoparticle of formation in water
Liquid adds volatile amine gas aqueous solution；Or luminous solution of gold nanoparticles is exposed in volatile amine gas, pass through
It visually observes variations in light, Fluorescence Spectrometer detection solution fluorescence variation and is changed using imaging system observation solution fluorescence.
9. the method that gold nanoparticle according to claim 8 quickly analyzes detection volatile amine, it is characterised in that：Volatilization
Property amine gas include in ammonia, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, propylamine or ethylenediamine it is a kind of with
On.
10. the method that gold nanoparticle according to claim 8 quickly analyzes detection volatile amine, it is characterised in that：Institute
The pH value for stating luminous solution of gold nanoparticles is 7-12.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113681022A (en) * | 2021-08-27 | 2021-11-23 | 华南理工大学 | Gold nano material without fluorescence background, preparation method thereof and method for in vitro histamine detection and in vivo histamine imaging |
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